The present invention provides compounds having the generic structure: ##STR2## wherein R.sub.1 and R.sub.2 taken together complete a cycloalkyl moiety or methyl, dimethyl or trimethyl substituted cycloalkyl moiety containing five or six carbon atoms in the ring and wherein R.sub.3 is C.sub.1 -C.sub.3 lower alkyl and R.sub.4 is methyl or hydrogen. Such compounds are provided by a novel process of our invention as shown by the reaction: ##STR3##
The compounds produced using the process of our invention are useful for their organoleptic properties in perfumes, perfumed articles, foodstuffs, foodstuff flavoring compositions, chewing gums, toothpastes, medicinal products, smoking tobaccos and smoking tobacco flavoring compositions, substitute smoking tobaccos and substitute smoking tobacco flavoring compositions.
In the perfumery art, there is a considerable need for substituents having sweet, fruity (figgy, raspberry-like), floral/rose-like, honey-like, rich, fruity (apple), green, floral/herbaceous, minty, camphoraceous, green, orris, leathery, earthy and peppery nuances with tobacco undertone. Specifically described herein are materials having such organoleptic profiles but which do not discolor with age. Such fragrance materials have a wide utilization in the presence of perfume compositions. A limited amount of such materials that give rise to these properties alone or in combination is available from natural sources, but the natural materials are subject to wide variations in quality, or are expensive and/or often in critically short supply.
In addition, there is a continuing search for food flavor compositions which can vary, fortify, modify, enhance, augment or otherwise improve the flavor and/or aroma of foodstuff, medicinal products, toothpastes, chewing gums and chewing tobaccos. To be satisfactory, such compositions should be stable, non-toxic and blendable with other ingredients to provide their own unique flavor and aroma nuances without detracting from the co-ingredients of the formulations in which they are used. Preferably, such compositions should be naturally occurring or present in natural foodstuffs so that their ingestible safety can be readily recognized. These materials should be capable of being synthesized in a simple and economical manner. The need for safe flavors in the raspberry, plum, strawberry and fruit juice-like flavor area is well known particularly in the ice cream and yogart flavor areas. More specifically, there is a need for the development of non-toxic materials which can replace natural materials not readily available having floral, green, fruity, sweet, estery, strawberry-like and ionone-like aroma nuances with sweet, floral, green/berry, strawberry-like, plum-like, fruit juice-like, raspberry juice-like, green, bitter, fruity, estery, earthy, astringent and ionone-like flavor nuances.
In the tobacco flavoring art (pertaining to smoking tobaccos and substitute smoking tobaccos) there is a considerable need for adjuvants for smoking tobacco and substitute smoking tobacco having sweet, minty, cooling, spicey, anisic, berry-like, fruity, pineapple-like, woody, green, pepper-like and dill-like aromas and tastes prior to smoking and on smoking in both the main stream and in the side stream and resulting from adding the adjuvants to tobacco per se, to the wrapper or to the filter or to combinations of the parts of the smoking tobacco article.
The instant invention provides the foregoing which the prior art has heretofore failed to provide. Furthermore, nothing in the prior art shows the unexpected, unobvious and advantageous value for their organoleptic properties of the genus of compound defined according to the structure: ##STR4## wherein R.sub.1 and R.sub.2 taken together complete a cycloalkyl moiety or a methyl, dimethyl or trimethyl cycloalkyl moiety containing five or six carbon atoms in the ring and wherein R.sub.3 is C.sub.1 -C.sub.3 lower alkyl and R.sub.4 is methyl or hydrogen.
The prior art has already taught the reaction of alkyl substituted acetylene derivatives or mono-substituted acetylene derivatives to form ketones. Indeed, Stacy and Mikulec, Org. Synth. Coll., Vol. IV (1963) 13 teaches the reaction: ##STR5## but does not discuss the use of metallic catalysts alternative to those containing mercury for such a reaction. Beilstein, Vol. 8, Supplement 3 teaches the reaction: and Johnson "The Chemistry of Acetylenic Compounds", Vol. I, Edward Arnold & Company, London, 1946 at page 103 teaches the reaction: ##STR6##
Nothing in the prior art shows the use in such a reaction of a silver ion catalyst without the addition of mineral acid. The silver is recoverable by precipitation of such salts as silver chloride or silver bromide. Such a mild acetylenic hydration is known in cases where catalysis using mercury compounds is used but use of silver is greatly advantageous particularly since mercury is toxic and there is a great likelihood of the mercury compound to contaminate equipment and create various hazardous situations.
Arctander "Perfume and Flavor Chemicals (Aroma Chemicals)", Vol. I, (1969), at monograph No. 37 discloses the use of acetyl cyclohexanol in perfumery and in perfumed articles indicating that acetyl cyclohexanol having the structure: ##STR7## has a camphoraceous, minty, herbaceous, somewhat floral odor. Arctander further indicates that this material is produced by "hydration of 1-ethynyl-cyclohexanol".
United Kingdom Pat. No. 1,344,653 published on Jan. 23, 1974 discloses the use in perfumery of certain carbo cyclic odorants possessing the following structure: ##STR8## where R' is hydrogen or methyl, R" is hydrogen or C.sub.1 -C.sub.3 alkanoyl, R"' is butyl, n is 0, 1 or 2, Z is one of the radicals --C.tbd.C--, --CH.dbd.CH-- or --CH.sub.2 --CH.sub.2 --.
Neither the Arctander disclosure nor the Givaudan United Kingdom Pat. No. 1,344,653 disclosure teaches either explicitly or implicitly the unexpected, unobvious and advantageous properties of the compounds of the instant application.